Process for preparing sulphonic acids and sulphonates

ABSTRACT

A process for separating sulphonic acids from a paraffin sulphonic acid solution containing in addition to the paraffin sulphonic acids, sulphonic acid, water and optionally non-sulphonated paraffins by mixing the solution with a slightly polar solvent having solubility in water of less than 7 percent to form an aqueous phase and an organic phase, separating the phases, neutralizing the organic phase and recovering the paraffin sulphonic acids from the neutralized organic phase.

This application is a continuation-in-part of our copending application Ser. No. 732,120, filed Oct. 13, 1976, now abandoned, which was a continuation-in-part of application Ser. No. 645,092 filed on Dec. 29, 1975, now abandoned, which, in turn, was a continuation of application Ser. No. 507,246, filed on Sept. 18, 1974, now abandoned, which was a continuation of application Ser. No. 169,145 filed Aug. 4, 1971, now abandoned.

The present invention concerns an improved process for separating paraffin sulphonic acids contained in an untreated sulphonic solution which also includes, in addition to these acids, sulphuric acid, water and non-sulphonated paraffins.

Certain sulphonic acids derived from hydrocarbons, and more specifically those obtained from linear paraffins, are subject to deterioration as a result of biological action, even at low temperature.

This makes such products particularly suitable for use as detergents, since they can be discharged into rivers or sea without causing any serious pollution of the aqueous environment that could harm aquatic flora and fauna.

These paraffin sulphonic acids can be produced by various methods, and in particular by the "sulphoxidation method," in which sulphur dioxide and oxygen are made to act simultaneously on paraffins, in particular linear paraffins, in the presence of photoactive radiations. A suitable amount of water is added, to extract the paraffin sulphonic acids out of the reaction mixture.

The untreated sulphonic solution, extracted from the reaction zone, which contains the paraffin sulphonic acids produced, sulphuric acid, water and a certain amount of paraffins which have not reacted, is treated in order to recover the sulphonic acids.

An existing method of performing this separation involves the addition to the reaction mixture from the sulphonation reactor of a polar light organic solvent that will not mix with paraffins such as methanol, ethanol or light esters, to bring about separation of the solution into a hydrocarbon phase and a paraffin-free aqueous organic phase containing the sulphonic acids and sulphuric acid in solution, and then neutralization of the aqueous-organic phase by means of an alkaline hydroxide, to separate out the sulphuric acid in the form of sulphate, which is removed by filtration, and finally, treatment of the aqueous-organic solution with an alkaline salt, in order to salt out the sulphonic acids or/and sulphonates.

This process has proved uneconomical, because of the high consumption of alkaline hydroxide needed to convert the sulphuric acid into sulphate, and the serious losses of sulphonates or sulphonic acids that occur during filtration of the sulphate. In addition, use of the process on an industrial scale, which, to be economic, requires continuous filtration of the sulphate, involves difficulties arising from the possibility of frequent clogging of the filters.

Another existing process consists of removing part of the sulphuric acid contained in the reaction mixture from the sulphonation reactor before extracting the paraffin sulphonic acids. The process involves rapid evaporation of the reaction mixture by heating up to 180° C., causing separation of the mixture into an upper layer containing the paraffins and sulphonic acids, and a lower layer of aqueous sulphuric acid which is then removed.

This process is not completely satisfactory either, because the heating required for evaporation of the reaction mixture causes fairly marked deterioration of the sulphonic acids, affecting the quality of the final product.

The present invention provides a remedy for the drawbacks of these existing processes, by making it possible to separate substantially all of the sulphuric acid from the paraffin sulphonic acids without the formation of an alkaline sulphate, and deterioration of the sulphonated products. Additionally, the invention provides a method for the recovery of the sulphonic acids as alkaline sulphonates in the form of free-flowing, substantially anhydrous and non-caking particles.

The process according to the invention for separating sulphonic acids from a paraffin sulphonic acid solution containing in addition to said paraffin sulphonic acids, sulphuric acid, water and optionally, non-sulphonated paraffins, comprises the following steps:

(a) admixing with the paraffin sulphonic acid solution at least one slightly polar solvent selected from the group consisting of aliphatic and cycloaliphatic ethers, esters, ketones and ketoesters containing at least 5 carbon atoms, having a solubility in water less than 7% by weight and which forms an azeotrope with water, thereby forming a mixture having an organic phase containing paraffin sulphonic acids dissolved therein and an aqueous phase containing sulphuric acid.

(b) separating said organic phase from said aqueous phase,

(c) neutralizing said separated organic phase by admixture with a composition selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal carbonates and mixtures thereof thereby converting the sulphonic acids present in said separated organic phase into sulphonates. The ratio of the amount of water to the amount of slightly polar solvent in said neutralized phase, preferably controlled or adjusted if necessary so that said ratio is at most equal to the corresponding ratio for the azeotrope which forms between water and the slightly polar solvent, then

(d) removing the volatile components from the neutralized organic phase to recover the sulphonates under temperature and pressure conditions to maintain said sulphonates in a molten state. The molten sulphonate product can be solidified and comminuted into particulate form or can be solidified in particulate form.

The slightly polar solvents useful in the process according to the present invention are selected from the group consisting of aliphatic or cycloaliphatic ethers, esters, ketones and ketoesters containing at least five carbon atoms, which have a solubility in water less than 7% by weight and which form an azeotrope with water. Among these compounds, those containing from 5 to 12 carbon atoms and having a solubility in water less than 5% by weight are preferred. In particular the slightly polar solvents useful in the process according to the invention can be selected from the group consisting of alkanones, cycloalkanones, aliphatic ethers, cycloaliphatic ethers; alkyl alkanoates, cycloalkylalkanoates, alkyl cycloalkanoates, and aliphatic ketoesters, which have at least five carbon atoms and preferably from five to 12 carbon atoms and which have a solubility in water less than 7% by weight and preferably less than 5% by weight.

Examples of ethers useful in the present invention include di n-propyl oxide, di isopropyl oxide, di isobutyl oxide, methyl heptyl oxide, diamyl oxide, di isoamyl oxide, di butyl oxide and the like. The alkanones and cycloalkanones include for example methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl nonyl ketone, diethyl ketone, dibutyl ketone, diisobutyl ketone, diamylketone, cyclooctanone, cycloheptanone and the like. Examples of useful esters and ketoesters include ethyl butyrate, n-butyl butyrate, amyl acetate, butylacetate, butyl acetyl acetate, isoamyl acetate, propylacetate and the like.

The amount of slightly polar solvent or mixture of such solvents added to the sulphonic acid solution in order to bring about separation of the sulphonic acid, generally ranges from 10 to 150 parts by weight to 100 parts by weight of the sulphonic acid solution, and preferably from 30 to 100 parts by weight to 100 parts by weight of said solution.

When the sulphonic acid solution contains some unreacted paraffins, said paraffins may be removed from the mixture containing the sulphonic acids before or after separation of the sulphuric acid, by adding a strongly polar liquid, such as methanol, ethanol, low molecular weight carboxylic acids, acetone, sulphoxides, which dissolves in water and does not mix with the paraffins, to cause them to salt out.

The mixture containing the sulphonic acids to which the strongly polar liquid is added can be the untreated sulphonic acid solution, if the paraffins are removed before separation of the sulphuric acid, or the organic phase containing the sulphonic acids in solution in the slightly polar solvent, if removal of the paraffins takes place after separation of the sulphuric acid.

The amount of strongly polar liquid added to the mixture containing the sulphonic acids generally ranges from 10 to 90% of the weight of the mixture containing the sulphonic acid and is preferably equal to about 60% of this weight.

When the unreacted paraffins are removed from the untreated sulphonic acid solution, the strongly polar liquid is usually separated from the substantially paraffin-free sulphonic solution before treatment with the slightly polar solvent.

According to the invention the organic phase containing the paraffin sulphonic acids dissolved in the slightly polar solvent is neutralized and the ratio of the amount of water to the amount of slightly polar solvent in said neutralized phase is controlled so that said ratio is at most equal to, and preferably less than the corresponding ratio for the azeotrope which forms between water and the slightly polar solvent. The neutralized organic phase is heated to remove the volatile components therefrom and to obtain the sulphonates as a molten mass which can be cooled and comminuted into particles.

Suitable neutralizing agents include hydroxides and carbonates of alkali-metals, particularly sodium and potassium and oxides, hydroxides and carbonates of alkaline-earth metals, particularly calcium, or mixtures of the foregoing and the like.

These agents may be used in solid form, or in alcoholic or aqueous solutions. The neutralizing agents are generally used in proportions at least sufficient to neutralize all the sulphonic acids, and preferably in a slight excess of the agent in relation to the stoichiometric proportion.

As previously indicated, while neutralizing the organic phase or after the neutralization has been performed but before the volatile solvents are separated from the neutralized phase, the ratio of the amount of water to the amount of slightly polar solvent in the neutralized phase is preferably adjusted so that the value of said ratio is at most equal to, and preferably less than the value of the corresponding ratio for the azeotrope which forms between water and the slightly polar solvent. The adjustment can be performed by merely determining the water content of the neutralized organic phase and if the determined content is higher than the content which corresponds to the azeotrope between water and the slightly polar solvent, a sufficient quantity of slightly polar solvent is added to the neutralized organic phase so that its water content is brought back to a value which does not exceed the content for said azeotrope. It is also possible to adjust the ratio of the amount of water to the amount of slightly polar solvent in the neutralized organic phase by determining the water content of the organic phase to be neutralized and then adding to said phase the neutralizing agent in the most appropriate form, namely in solid form or as a solution of suitable concentration in the slightly polar solvent or in water so that the total water content of the neutralized solution, which includes the water content of the organic phase to be neutralized together with the water content resulting from the neutralization reaction and possibly the water content from the added water if an aqueous solution of neutralizing agent is used, is at most equal to, and preferably less than the water content for the azeotrope. This control of the ratio of the amount of water to the amount of slightly polar solvent in the neutralized phase, performed either during the neutralization or after carrying out the neutralization, insures that a complete removal of the water is obtained during the evaporation step of the neutralized organic phase and accordingly that a substantially anhydrous sulphonate mass is produced.

Evaporation of the neutralized organic phase is carried out under pressure and temperature conditions that will ensure that the sulphonate is molten. The operation is generally performed at atmospheric pressure, though it is possible to work under a vacuum of varying force. The temperature required is dependent upon the melting point of the sulphonate.

In a variant involving the treatment of the organic solution of the sulphonic acids in the slightly polar solvent from which the paraffins have been removed by treatment with a strongly polar liquid after separation of the sulphuric acid, the polar liquid is recovered by distillation after the neutralization step and before evaporation of the slightly polar solvent. The strongly polar liquid is generally water soluble.

The alkali-metal or alkaline earth metal sulphonate collected in molten form after evaporation of the volatile solvents from the neutralized organic phase is substantially free from water, slightly polar solvent and unreacted paraffins. It can easily be converted into a free-flowing, practically anhydrous and non-caking white powder.

This powder can be handled easily and is particularly well-adapted to pneumatic conveyance. It can be stored without difficulty and is easily incorporated into detergents sold commercially in powder form.

The particle size of this powder can vary widely, depending on the use to which it is to be put. For normal purposes, it is preferably between 40 and 600 microns.

The powder may be prepared by any process enabling a powder of given particle size to be obtained from a molten mass. The mass of molten sulphonate can be solidified in the form of flakes, for example, and the flakes ground to the particle size required in a suitable device, such as a disintegrator with blades rotating at high speed.

The mass of molten sulphonate can also be atomized in a current of cold gas, inert in relation to the sulphonate, such as an air current. To achieve this atomization, the molten sulphonate may be injected under pressure in a spray nozzle, or divided by centrifugal force in an appliance revolving at high speed. Atomization is preferable when roughly spherical particles are required. The temperature chosen for supply of the atomization system generally depends on its dispersal capacity. Preferably, it should be a temperature at which the molten sulphonate has a sufficiently low viscosity. In the case of the atomization of paraffin sodium sulphonates, for instance, the atomization system is supplied at a temperature of preferably between 150° and 200° C., since within this range the paraffin sodium sulphonates have a viscosity of between 100 and 50 poises.

The process according to the present invention is particularly useful for the treatment of untreated sulphonic solutions resulting from sulphoxidation of normal paraffins, the molecules of which contain between 7 and 30, and preferably between 10 and 20 carbon atoms.

The invention is illustrated by, while not being confined to the following example.

EXAMPLE

A photochemical reactor, supplied with a mixture of linear paraffins, and with water, sulphur dioxide and oxygen, produces an untreated sulphonic solution with the following composition in percentage weights:

    ______________________________________                                         Sulphonic acid          20.6%                                                  Sulphuric acid           7.2%                                                  Non-sulphonated paraffins                                                                              31%                                                    Water                   41.2%                                                  ______________________________________                                    

After the gas has been removed from this solution, variable amounts of slightly polar solvent are added to 1,000 g of the solution. The mixture is stirred in a contactor, then directed to a decanting apparatus where a heavy aqueous phase containing sulphuric acid separates out. The sulphonic acids contained in the organic light phase which also contains some water are next neutralized by means of a 50% sodium hydroxide (12 N) solution, a slight excess compared with the stoichiometric quantity being used. A solution of sodium sulphonate in the organic phase is obtained for which the ratio of the amount of water to the amount of slightly polar solvent is less than the corresponding ratio for the azeotrope between water and the slightly polar solvent.

The Table hereafter shows the percentage weights of sulphuric acid salted out in the aqueous phase depending on the type of slightly polar solvent, the percentage weights in relation to the untreated sulphonic acid solution, and also the water to slightly polar solvent weight ratio in the neutralized organic phase.

The solution of sodium sulphonate in the organic phase is conveyed to an evaporator functioning at about 175° C., in which the slightly polar solvent and remaining water are separated out. The paraffin is then evaporated in a thin-layer evaporator at sufficient temperature and pressure to remove all the paraffin.

The molten sulphonate left the evaporator at a temperature of about 200° C. with a viscosity of about 50 poises.

The molten sulphonate was solidified on a drum cooled internally by circulating water and the flakes obtained with this drum were then ground in a disintegrator equipped with high-speed revolving blades.

The sulphonate powder which was obtained in the various tests in an amount ranging from 220 to 226 g, consisted of rounded particles with a particle-size from 70 to 400 microns. Said powder was white, substantially anhydrous and free from paraffin. No lumps were found to form even after prolonged storage.

                  TABLE                                                            ______________________________________                                                   % weight of             Water to                                               slightly     %          solvent                                                polar sol-   sulphonic  weight                                                 vent in relation                                                                            acid salted                                                                               ratio in the                                 Slighty   to untreated sul-                                                                           out in     neutralized                                  polar solvent                                                                            phonic solution                                                                             aqueous phase                                                                             organic phase                                ______________________________________                                         Methylpropyl-                                                                  ketone    34           79         0.20                                                   42           82         0.17                                                   85           98.5       0.074                                        Methyl Isobutyl                                                                ketone    42           83         0.28                                                   82           96.5       0.081                                        Diisopropyl                                                                    oxide     37           68         0.04                                                   75           78.5       0.04                                         Propyl acetate                                                                           92           88         0.10                                         Butyl acetate                                                                            36           78         0.37                                                   45           81         0.26                                                   91           83         0.12                                         Amyl acetate                                                                             44.5         84         0.24                                                   90           89         0.11                                         Isoamyl acetate                                                                          44           83         0.26                                                   89           84         0.10                                         Ethyl butyrate                                                                           45           77         0.21                                                   90           83         0.125                                        ______________________________________                                     

What is claimed is:
 1. A process for separating the sulphonic acids in an untreated paraffin sulphonic solution containing in addition to said paraffin sulphonic acids, sulphuric acid, water, and non-sulphonated paraffins, which comprises:(a) admixing with the paraffin sulphonic acid solution, at least one slightly polar solvent selected from the group consisting of alkanones, cycloalkanones, aliphatic ethers, cycloaliphatic ethers, alkyl alkanoates, cycloalkylalkanoates, alkylcycloalkanoates and aliphatic ketoesters containing at least 5 carbon atoms, having a solubility in water less than 7% by weight, which forms an azeotrope with water, thereby forming a mixture having an organic phase containing paraffin sulphonic acids dissolved therein and an aqueous phase containing the sulphuric acid; (b) separating said organic phase from said aqueous phase; (c) neutralizing said separated organic phase by admixture with a composition selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkaline earth metal oxides, alkaline earth metal hydroxides, and alkaline earth metal carbonates thereby converting the sulphonic acids present in said organic phase into sulphonates, and forming a neutralized organic phase wherein the ratio of the amount of water to the amount of slightly polar solvent in said neutralized phase is at most equal to the corresponding ratio for the azeotrope which forms between water and the slightly polar solvent; and (d) removing the volatile components from the neutralized organic phase to recover the sulphonates under temperature and pressure conditions whereby said sulphonates are in a molten state.
 2. A process according to claim 1, wherein from 10 to 150 parts by weight of said slightly polar solvent is added per 100 parts by weight of said untreated paraffin sulphonic acid solution and said organic phase is neutralized with at least a stoichiometric amount of the selected alkali metal or alkaline earth metal compositions.
 3. A process according to claim 1, wherein said slightly polar solvent is added to said untreated sulphonic acid solution in an amount from about 30 to 100 parts by weight to 100 parts by weight of said untreated sulphonic acid solution.
 4. A process according to claim 1, wherein said sulphonic acids are derived from normal paraffins having 7 to 30 carbon atoms.
 5. A process according to claim 1, wherein said sulphonic acids are derived from normal paraffins having 10 to 20 carbon atoms.
 6. A process according to claim 1, which includes the step of separating paraffins from said untreated sulphonic acid solution prior to the addition of said slightly polar solvent thereto, by treating said solution with a water soluble polar liquid which does not mix with the paraffins and causes the separation thereof.
 7. A process according to claim 1 wherein said molten sulphonate mass is cooled into flakes, which are then ground to the required particle size.
 8. A process according to claim 1 wherein the water solubility of the slightly polar solvent is less than 5% by weight.
 9. A process according to claim 1, wherein said slightly polar solvent contains from 5 to 12 carbon atoms and has a solubility in water less than 5% by weight.
 10. The process of claim 1 wherein the molten sulphonate is cooled and comminuted into particulate form. 